CN104032136A - Method for recycling copper, indium, gallium and selenium from waste material - Google Patents
Method for recycling copper, indium, gallium and selenium from waste material Download PDFInfo
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Abstract
The invention provides a method for recycling copper, indium, gallium and selenium from a waste material. The method comprises the steps: by using a CIGS (copper, indium, gallium and selenium) waste material as an anode, performing electrolysis to recycle gallium, leaching precipitates such as anode mud and the like, and performing displacement or electro-deposition on leaching liquid to recycle indium; performing acid leaching on leaching residues, performing acid regulation by using alkali, and respectively adding reducing agents, namely selenium and copper. The method is simple, and reclaimed indium, copper and gallium can be recycled for preparing a CIGS target material. The method provided by the invention is used for performing electrolysis by using the CIGS waste material as the anode, directly performing electro-deposition on gallium, and then respectively separating and recycling indium, copper and selenium by using an ordinary chemical separation method, therefore, the method is an excellent method capable of recycling high-purity indium and gallium very simply and efficiently. In industrial production, the recovery rate of indium exceeds 99%, the grade of precise indium reaches 99.995%, the recovery rate of copper reaches 98.8%, the recovery rate of gallium is more than 99%, and the recovery rate of selenium reaches 98%.
Description
Technical field
The resource utilization recycling field that the present invention relates to Non-ferrous Metallurgy field and solid waste, relates in particular to a kind of method that reclaims copper-indium-galliun-selenium from waste material.
Background technology
Copper-indium-galliun-selenium (CIGS) thin film solar cell has high photoelectric efficiency, has good development potentiality.Its production method has vacuum splashing and plating method, distillation method and antivacuum coating method, no matter adopt which kind of making method, in its making processes, all can produce the waste material of some copper-indium-galliun-seleniums, and in these waste materials except containing heavy metal copper, also contain the rare metals such as indium, gallium and selenium.For being conducive to the sustainable utilization of the rare metals such as indium, gallium and selenium and heavy metal copper, need to separating and reclaim respectively, to facilitate recycle further, to ensure the Sustainable development of copper-indium-galliun-selenium film solar cell material.In prior art, the recovery method of copper-indium-galliun-selenium waste material mainly contains wet method or the pyrorefining combined methods such as acid-soluble method, extraction process, oxidation distillation method.For example: publication number is that the Chinese patent application of CN102296178 A discloses a kind of method that reclaims copper-indium-galliun-selenium from waste material, specifically discloses and utilizes the mixed solution of hydrochloric acid and hydrogen peroxide to dissolve the method that includes copper-indium-galliun-selenium metal-powder.The method is used hydrazine reduction selenium, with indium metal displacement copper, and indium is separated with gallium in conjunction with dispersion strip liquor by support type liquid film.There is following shortcoming in the method: 1, the leaching yield of metal is not high, and adopt hydrazine to make reductive agent, because of the too high high cost that makes of hydrazine price, do not have economic feasibility.2, at copper indium content quite and in solution, copper indium concentration is higher in the situation that, still with rare metal indium displacement heavy metal copper, this method is science not, more do not there is economic feasibility, because extraction process long flow path, the multiple working procedures such as leaching-extracting-back extraction-displacement-pressure group need be set, cost is high, indium recovery is lower, adopt extraction process to reclaim indium is generally for containing indium lower (the mass percentage content <5% of indium in raw material) in raw material simultaneously, and the more material of impurity element kind in leach liquor, also be just to adopt under the prerequisite that adopts other method to be difficult to separate, and in this patent application, be still to adopt extraction process enrichment and purification indium at indium content under up to 20% prerequisite, and improper.
The United States Patent (USP) of notification number US5779877 discloses a kind of recovery method of copper indium diselenide photovoltaic waste material, specifically disclose: comprise fragmentation, nitric acid leaching, two electrolysis separating coppers, selenium and indium, then evaporation, decomposition obtains the hopcalite of indium and zinc, oxidation distillation separating copper and selenium.The method long flow path, two electrolysis processes are difficult to control, and oxidation distillation separates not thorough, selenium recovery is low, and the finished product are only metallic compound, needs further processing could obtain rare metal, the suitability of the method is restricted simultaneously, can not solve the recovery problem of gallium.Notification number is the recovery method that the United States Patent (USP) of US3954951 discloses selenium, under low temperature (20 DEG C) condition, utilizes hydrazine to be dissolved in selenous acid in first (second) alcohol and to restore the selenium of amorphous.Notification number is the recovery method that discloses gallium in I268802 TaiWan, China patent, utilizes supportive liquid film from gallium arsenide waste, to carry out the recovery of gallium.From the foregoing, the technique that reclaims copper, indium, gallium and selenium in waste material is quite complicated, and cost is higher, is subject to certain limitation in industrial application.Therefore, need to desire most ardently solution and there is the comprehensive recovering process that cost recovery is lower, technique simple, be easy to a kind of copper-indium-galliun-selenium waste material of the feature of production application and high efficiente callback copper, indium, gallium and selenium.
Therefore, how from copper-indium-galliun-selenium waste material, separating also high efficiente callback valuable metal copper, indium, gallium and selenium is to need a further difficult problem for exploration.
Summary of the invention
The present invention reclaims complex process and the higher defect of cost of copper, indium, gallium and selenium in order to solve existing copper-indium-galliun-selenium, thereby the copper-indium-galliun-selenium that a kind of method is simple, cost is low recovery method is provided.
The invention provides a kind of method that reclaims copper-indium-galliun-selenium from waste material, the method comprises the following steps:
S1, recovery gallium: be placed on copper-indium-galliun-selenium waste material as anode in electrolytic solution and carry out electrolysis, make gallium galvanic deposit reclaim gallium to negative electrode, pH >=10 of described electrolytic solution;
S2, reclaim indium: indium hydroxide precipitation is extracted out together with the copper selenium anode sludge and again dissolve and form solution of indium and copper selenium leached mud, indium is reclaimed in pH≤3 of described solution of indium from solution of indium;
S3, recovery selenium: copper selenium leached mud is leached completely with acid, and regulate and obtain leach liquor with alkali, leach liquor is reduced into selenium to selenium powder and reclaims selenium with reductive agent;
S4, recovery copper: step S3 is reclaimed to the solution obtaining after selenium and add reductive agent reduction to reclaim copper or step S3 reclaimed to the electrolysis of solutions recovery copper obtaining after selenium.
Reaction principle of the present invention is:
The principal reaction formula of gallium electrolysis:
On anode: Ga-3e → Ga
3+(1)
In-3e→In
3+……………………………………………………(2)
On negative electrode: Ga
3++ 3e → Ga ... (3)
In
3++3NaOH→3Na
++In(OH)
3↓…………………………………………(4)
In(OH)
3+3H
+→3H
2O+In
3+………………………………………………(5)
2In+6H
+→3H
2↑+2In
3+……………………………………………………(6)
The principal reaction formula of indium electrolysis:
On anode: 2OH
--2e → H
2o+1/2O
2↑ ... (7)
On negative electrode: In
3++ 3e → In ... (8)
3Zn+2In
3+→2In+3Zn
2+…………………………………………………?(9)
Zn+2H
+→H
2↑+Zn
2+……………………………………………………?(10)
3Cu+8HNO
3→4H
2O+3Cu(NO
3)
2+2NO↑………………………………(11)
Cu+4HNO
3→2H
2O+Cu(NO
3)
2+2NO
2↑…………………………………(12)
2HNO
3+Se→2NO↑+H
2SeO
4……………………………………………(13)
6HNO
3+Se→6NO
2↑+H
2SeO
4+2H
2O……………………………………(14)
2H
2SeO
4+3N
2H
5 +→2Se↓+3N
2↑+8H
2O+3H
+…………………………(15)
The principal reaction formula of cupric electrolysis:
On anode: 2OH
--2e → H
2o+1/2O
2↑ ... (16)
On negative electrode: Cu
2++ 2e → Cu ... (17)
Cu
2＋+Zn→Cu+Zn
2+………………………………………………………(18)
The present invention utilizes each metallics Standard Electrode Potentials difference to be recycled, and the solubleness of metal ion in solution is because of the different characteristics that change of pH value, realizes the separation of each material.Concrete separating step is: in copper-indium-galliun-selenium electrolytic process, the copper selenium of Standard Electrode Potentials calibration generates the anode sludge, and indium, gallium enter electrolytic solution with the form of ion, and do not generate colloidalmaterial, can make gallium separate out smoothly at negative electrode through electrodeposition; Electrolytic process can carry out continuously, and to electrolytic condition, without particular requirement, and indium ion and hydroxide ion generate indium hydroxide precipitation under certain pH value, sink to bottom of electrolytic tank together and separate with gallium with the anode sludge; Because the Standard Electrode Potentials of element Cu and Se is greater than 0, and the Standard Electrode Potentials of In is less than 0, and indium hydroxide and indium metal dissolve in the strong acid such as non-oxidizing sulfuric acid and hydrochloric acid, and simple substance Cu and Se are insoluble in the strong acid such as non-oxidizing sulfuric acid and hydrochloric acid, indium hydroxide is insoluble oxyhydroxide, only under lower pH condition, just dissolve (pH≤3), utilizes above-mentioned principle can further realize separating of indium and copper selenium.Therefore, in the present invention, in the step of copper-indium-galliun-selenium electrolytic recovery gallium, control pH >=10 of electrolytic solution, the indium ion that electrolysis is generated has generated precipitation indium hydroxide and has separated with gallium; And in subsequent step, continue to utilize above-mentioned characteristic, make indium hydroxide precipitation and the copper selenium anode sludge in leaching process, control pH≤3, make indium hydroxide solution enter solution, and with the separating of copper selenium; And the separation of copper selenium in leached mud is the difference that utilizes the Standard Electrode Potentials of Cu, Se and reductive agent with reclaiming, select suitable reductive agent, Cu, Se are optionally reduced, thereby are separated and reclaim.
Beneficial effect of the present invention is:
In the present invention, carry out electrolytic recovery gallium using CIGS waste material as anode, the throw outs such as the anode sludge are by leaching, and leach liquor, by electrodeposition or displacement, reclaims indium; Leached mud is by acidleach, alkali acid adjustment, then add respectively reductive agent to reclaim respectively selenium and copper.The method indium, copper and gallium simple and that reclaim can utilize in the regeneration of preparation CIGS target.
The present invention uses CIGS waste material to carry out electrolysis as anode, and directly galvanic deposit gallium, then separates respectively and reclaim indium, copper and selenium with conventional chemical separation method, therefore, is the excellent process that can extremely simply and efficiently reclaim highly purified indium and gallium.In industrial production, the rate of recovery of indium exceedes 99%, and the grade of smart indium reaches 99.995%; The rate of recovery of copper reaches 98.8%, and output copper powder or other copper system product; The rate of recovery of gallium more than 99%, output essence gallium; The rate of recovery of selenium reaches 98%, generates thick selenium.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of method that reclaims copper-indium-galliun-selenium from waste material, the method comprises the following steps:
S1, recovery gallium: be placed on copper-indium-galliun-selenium waste material as anode in electrolytic solution and carry out electrolysis, make gallium galvanic deposit reclaim gallium to negative electrode, pH >=10 of described electrolytic solution;
S2, reclaim indium: indium hydroxide precipitation is extracted out together with the copper selenium anode sludge and again dissolve and form solution of indium and copper selenium leached mud, indium is reclaimed in pH≤3 of described solution of indium from solution of indium;
S3, recovery selenium: copper selenium leached mud is leached completely with acid, and regulate and obtain leach liquor with alkali, leach liquor is reduced into selenium to selenium powder and reclaims selenium with reductive agent;
S4, recovery copper: step S3 is reclaimed to the solution obtaining after selenium and add reductive agent reduction to reclaim copper or step S3 reclaimed to the electrolysis of solutions recovery copper obtaining after selenium.
The invention provides the method that reclaims valuable metal from CIGS waste material that reclaims gallium by CIGS waste material being carried out to electrolysis.By carry out electrolysis in electrolytic solution using CIGS waste material as anode, it is dissolved, make the form precipitation of indium with indium hydroxide, and copper selenium precipitates using metallic forms as the anode sludge, postorder operation is more easily separated respectively and reclaim.And the present invention reclaims the electrolytic solution of valuable metal gallium from CIGS waste material, mainly uses the basic solution such as sodium hydroxide and potassium hydroxide.The electrolytic solution that reclaims valuable metal indium mainly uses sulfuric acid or hydrochloric acid etc. not to have the strongly acidic solution of oxidisability.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, for can more effective recovery gallium and make indium precipitation, preferably, pH >=10 of the electrolytic solution described in step S1, more preferably 10-14.In the time that pH is less than 10, there is part Ga
3+can be precipitated out with the form of gallium hydroxide, reduce the rate of recovery of gallium.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, for can more effective recovery gallium, and indium be with indium hydroxide form precipitation, and preferably, the temperature of described electrolytic solution is 0-100 DEG C, more preferably 18-55 DEG C.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, owing to being used CIGS waste material, therefore the electrolytic condition such as current density can not be determined without exception, and current density is suitably selected to implement according to the amount of anode and its character.According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, the method that described step S2 reclaims indium is electrolysis or replacement(metathesis)reaction, more preferably electrolysis.Described electrolysis obtains indium metal, and described displacement is to adopt zinc metal sheet or aluminium flake displacement, obtains thick indium.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, described in step S2, the method for dissolved hydrogen Indium sesquioxide precipitation and the copper selenium anode sludge is for dissolving with sulfuric acid or hydrochloric acid, obtain solution of indium (being leach liquor) and copper selenium leached mud, initial acidity is that sulfuric acid is that 1.5-2.5mol/L or hydrochloric acid are 2-6mol/L, temperature is 50-80 DEG C, liquid-solid ratio is between 3-10, pH≤3 of solution of indium, applicant finds through experiment, within the scope of this, can ensure that indium hydroxide precipitation becomes cationic indium simple substance to dissolve completely with incomplete electrodeposition in anode, guarantee the high-recovery of indium.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, described in step S3, the method for dissolved copper selenium leached mud is for dissolving with acid, pH≤1.5 of the solution obtaining after dissolving, pH value is within the scope of this time, both can reduce sour consumption, and can also ensure the leaching yield of copper and selenium, thereby reduce costs.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, in order to ensure the leaching efficiency of selenium, preferably, the temperature of the leach liquor described in step S3 is 0-100 DEG C.In industrial production, consider the maximization of cost, in the time that pursuit leaching operation reduces costs, to increase the treatment capacity in the unit time simultaneously, thereby reduce whole production cost, therefore leach liquor temperature is preferably 60-85 DEG C.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, the acid described in step S3 is at least one in nitric acid, sulfuric acid and hydrochloric acid; Described alkali is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor and soda ash.Described acid can be good at making the selenium in copper selenium leached mud to leach, and described alkali can well be controlled the terminal pH of leach liquor, thereby is more conducive to reductive agent reduction selenium and becomes the effect of selenium powder.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, in order to improve reductive agent, selenium is reduced into the effect of selenium powder, preferably, the terminal pH of the leach liquor described in step S3 is 1-3, the restriction of above-mentioned scope can be saved the consumption of reductive agent in the reduction operation of follow-up selenium, improve the grade of thick selenium, thereby increase economic efficiency.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, the reductive agent described in step S3 is SO
2, Na
2sO
3, at least one in thiocarbamide and urea element.It is suitable that the Standard Electrode Potentials of above-mentioned reductive agent can make copper selenium separate, and wide material sources, and cost is low.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, preferably, the reductive agent described in described step S4 is at least one in zinc powder, iron powder and hydrazine hydrate.
According to the method that reclaims copper-indium-galliun-selenium from waste material provided by the present invention, in order to improve current efficiency, the known interpolation material known to can using conventionally, and the purity that adds not reduce indium and gallium of additive is prerequisite.When above-mentioned chemical treatment method reduction selenium and copper, the known reductive agent of reductive agent known to can using conventionally, reduces production costs the adding of reductive agent and the grade that improves copper and selenium is prerequisite.
Because produce without colloid in electrolytic process of the present invention, without the impact of considering that colloid is carried out continuously on electrolytic process, electrolyzer can use the electrolyzer of common electrolysis indium, gallium and copper, to equipment without particular requirement, without adopting the electrolyzer that is provided with ion-exchange membrane, electrolytic process can be continuous, simple to operate, and equipment cost is lower.As can be using the CIGS that treats electrolysis as anode, the corrosion resistant electrodes such as titanium plate carry out electrolysis as cathodic master plate, can avoid like this increase of impurity in anode or sneak into.
In preparation method of the present invention, sometimes in CIGS, also added a small amount of secondary composition, or lacked certain element, but as long as substantially taking CIGS as fundamental component, the present invention also can apply.
Below by specific embodiment, the present invention is further described.
Embodiment 1
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in sodium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is sodium hydroxide solution, and pH is 10, and electrolysis temperature is 55 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.998%.By the method, the rate of recovery of gallium reaches 99.35%.
2, indium separates and recycling step
Indium is formed to precipitation of hydroxide and copper selenium anode sludge Leaching in Hydrochloric Acid obtains sulphuric leachate and sulfuric acid leaching slag, the initial volumetric molar concentration of hydrochloric acid is 2mol/L, and liquid-solid ratio is 10, and temperature is 80 DEG C.Hydrochloric acid leachate is through indium electrolysis, the smart indium that the grade that obtains indium is 99.9972%, and the rate of recovery of indium reaches 99.37%.
3, copper selenium separates and recycling step
Leaching in Hydrochloric Acid slag is leached with nitric acid under 60 DEG C of conditions, leach completely rear use ammoniacal liquor and the acid adjustment of sodium hydroxide mixed solution, terminal pH is 1, adds reductive agent thiocarbamide, and in CIGS waste material, 98.2% selenium is reduced into selenium powder and reclaims.
Except adding the zinc powder of theoretical amount in liquid after selenium, make copper reduction, obtain copper metal, the rate of recovery of copper reaches 98.9%.
Embodiment 2
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in potassium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is potassium hydroxide solution, and pH is 12, and electrolysis temperature is 18 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.997%.By the method, the rate of recovery of gallium reaches 99.51%.
2, gallium separates and recycling step
Precipitation of hydroxide and the copper selenium anode sludge that indium is formed obtain sulphuric leachate and sulfuric acid leaching slag with sulfuric acid leaching, and the initial volumetric molar concentration of sulfuric acid is 1.5mol/L, and liquid-solid ratio is 10, and temperature is 80 DEG C.Sulphuric leachate is through indium electrolysis, the smart indium that the grade that obtains indium is 99.9982%, and the rate of recovery of indium reaches 99.43%.
3, copper selenium separates and recycling step
Sulfuric acid leaching slag is leached with nitric acid under 85 DEG C of conditions, leach the completely rear soda ash liquid acid adjustment of using, terminal pH is 3, adds reductive agent Na
2sO
3, in CIGS waste material, 98.84% selenium is reduced into selenium powder and reclaims.
Except adding the iron powder of theoretical amount in liquid after selenium, make copper reduction, obtain copper metal, the rate of recovery of copper reaches 99.2%.
Embodiment 3
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in potassium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is potassium hydroxide solution, and pH is 10, and electrolysis temperature is 25 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.9983%.By the method, the rate of recovery of gallium reaches 99.28%.
2, indium separates and recycling step
The precipitation of hydroxide that indium is formed and the copper selenium anode sludge leach and obtain hydrochloric acid leachate and Leaching in Hydrochloric Acid slag with hydrochloric acid soln, and the initial volumetric molar concentration of hydrochloric acid is 4mol/L, and liquid-solid ratio is 6, and temperature is 65 DEG C.Hydrochloric acid leachate adds zinc metal sheet to replace, the thick indium that the grade that obtains indium is 99.76%, and the rate of recovery of indium reaches 99.29%.
3, copper selenium separates and recycling step
Leaching in Hydrochloric Acid slag is leached with nitric acid under 70 DEG C of conditions, after leaching completely, use caustic lye of soda acid adjustment, terminal pH is 2, passes into reductive agent sulfurous gas, and in CIGS waste material, 98.8% selenium is reduced into selenium powder and reclaims.
Except liquid after selenium packs copper electrolysis cells electrolysis into, obtain acid copper, the rate of recovery of copper reaches 98.85%.
Embodiment 4
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in sodium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is sodium hydroxide solution, and pH is 12, and electrolysis temperature is 5 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.9974%.By the method, the rate of recovery of gallium reaches 99.27%.
2, indium separates and recycling step
Indium is formed to precipitation of hydroxide and copper selenium anode sludge sulphuric acid soln and leach and obtain sulphuric leachate and sulfuric acid leaching slag, the initial volumetric molar concentration of sulfuric acid is 2mol/L, and liquid-solid ratio is 6, and temperature is 65 DEG C.The solution of indium (being leach liquor) that sulfuric acid leaching obtains is replaced through aluminium, the thick indium that the grade that obtains indium is 99.658%, and the rate of recovery of indium reaches 99.60%.
3, copper selenium separates and recycling step
Sulfuric acid leaching slag is leached with nitric acid under 10 DEG C of conditions, after leaching completely, use ammoniacal liquor acid adjustment, terminal pH is 1.5, adds reductive agent thiocarbamide, and in CIGS waste material, 98.5% selenium is reduced into selenium powder and reclaims.
Except adding the hydration well of theoretical amount in liquid after selenium, make copper reduction copper, obtain copper powder, the rate of recovery of copper reaches 98.9%.
Embodiment 5
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in potassium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is potassium hydroxide solution, and pH is 14, and electrolysis temperature is 98 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.9983%.By the method, the rate of recovery of gallium reaches 99.46%.
2, indium separates and recycling step
Indium is formed to precipitation of hydroxide and copper selenium anode sludge hydrochloric acid soln and leach and obtain hydrochloric acid leachate and sulfuric acid leaching slag, the initial volumetric molar concentration of hydrochloric acid is 6mol/L, and liquid-solid ratio is 3, and temperature is 50 DEG C.Leaching in Hydrochloric Acid obtains solution of indium (being leach liquor) through indium electrolysis, the smart indium that the grade that obtains indium is 99.9969%, and the rate of recovery of indium reaches 99.34%.
3, copper selenium separates and recycling step
Leaching in Hydrochloric Acid slag is used under 98 DEG C of conditions to Leaching in Hydrochloric Acid, after leaching completely, is used ammoniacal liquor acid adjustment, terminal pH is 1.5, adds reductive agent thiocarbamide, and in CIGS waste material, 98.9% selenium is reduced into selenium powder and reclaims.
Except liquid after selenium packs copper electrolysis cells into, in salpeter solution, carry out electrorefining, make cupric ion electrodeposition become electrolytic copper, the rate of recovery of copper reaches 99.25%.
Embodiment 6
Using the waste material of 3 kilograms of CIGS as raw material, the composition of this raw material is: the weight percent of copper is 19.8%, and the weight percent of indium is 25.4%, and the weight percent of gallium is 5.7%, and surplus is selenium.
1, CIGS electrolysis step
Pack this raw material into gallium electrolyzer, in sodium hydroxide solution, carry out electrorefining.
Electrolytic condition is: electrolytic solution is sodium hydroxide solution, and pH is 15, and electrolysis temperature is 45 DEG C.
The galvanic deposit of result gallium is to cathode side, the smart gallium that the grade that can obtain thus gallium from the waste material of CIGS is 99.9968%.By the method, the rate of recovery of gallium reaches 99.41%.
2, indium separates and recycling step
Indium is formed to precipitation of hydroxide and copper selenium anode sludge sulfuric acid leaching obtains sulphuric leachate and sulfuric acid leaching slag, the initial volumetric molar concentration of sulfuric acid is 2.5mol/L, and liquid-solid ratio is 3, and temperature is 50 DEG C.Sulphuric leachate is through gallium electrolysis, the smart indium that the grade that obtains indium is 99.9984%, and the rate of recovery of indium reaches 99.33%.
3, copper selenium separates and recycling step
Sulfuric acid leaching slag is used under 75 DEG C of conditions to sulfuric acid leaching, leached the completely rear soda ash liquid acid adjustment of using, terminal pH is 2.4, adds reductive agent urea element, and in CIGS waste material, 99.1% selenium is reduced into selenium powder and reclaims.
Except liquid after selenium packs copper electrolysis cells into, in salpeter solution, carry out electrorefining, make cupric ion electrodeposition become electrolytic copper, the rate of recovery of copper reaches 99.14%.
Comparative example 1
Adopt the method for CN102296178 A embodiment 7 to reclaim copper-indium-galliun-selenium, the rate of recovery that result is indium is 97.7%, and the rate of recovery of gallium is 98.05%, and the rate of recovery of selenium is 98.4%, and the rate of recovery of copper is 97.9%.
From the contrast of embodiment 1-6 and comparative example 1, find, the CIGS waste materials such as the CIGS tailing that the present invention produces while adopting copper, indium, gallium and selenium alloy belong to sputtering target or manufacture carry out electrolysis as anode, can be simply and high efficiente callback copper, indium and selenium when high efficiente callback gallium, aspect environmental protection and resource reutilization, industrial applications, there is remarkable advantage.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a method that reclaims copper-indium-galliun-selenium from waste material, is characterized in that, the method comprises the following steps:
S1, recovery gallium: be placed on copper-indium-galliun-selenium waste material as anode in electrolytic solution and carry out electrolysis, make gallium galvanic deposit reclaim gallium to negative electrode, pH >=10 of described electrolytic solution;
S2, reclaim indium: indium hydroxide precipitation is extracted out together with the copper selenium anode sludge and again dissolve and form solution of indium and copper selenium leached mud, indium is reclaimed in pH≤3 of described solution of indium from solution of indium;
S3, recovery selenium: copper selenium leached mud is leached completely with acid, and regulate and obtain leach liquor with alkali, leach liquor is reduced into selenium to selenium powder and reclaims selenium with reductive agent;
S4, recovery copper: step S3 is reclaimed to the solution obtaining after selenium and add reductive agent reduction to reclaim copper or step S3 reclaimed to the electrolysis of solutions recovery copper obtaining after selenium.
2. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the temperature of described electrolytic solution is 0-100 DEG C, and the pH of described electrolytic solution is 10-14.
3. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the method that described step S2 reclaims indium is electrolysis or displacement, described in be replaced into and adopt zinc metal sheet or aluminium flake displacement indium.
4. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the method for dissolved hydrogen Indium sesquioxide precipitation and the copper selenium anode sludge is for to dissolve with acid described in step S2, and described acid is sulfuric acid or hydrochloric acid.
5. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 4, is characterized in that, in step S2, while dissolving with acid, initial acidity is sulfuric acid 1.5-2.5mol/L or hydrochloric acid 2-6mol/L, and temperature is 50-80 DEG C, and liquid-solid ratio is 3-10.
6. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, acid is at least one in nitric acid, sulfuric acid and hydrochloric acid described in step S3; Described alkali is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor and soda ash.
7. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the temperature of the leach liquor described in step S3 is 0-100 DEG C.
8. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the reductive agent described in step S3 is SO
2, Na
2sO
3, at least one in thiocarbamide and urea element.
9. the method that reclaims copper-indium-galliun-selenium from waste material according to claim 1, is characterized in that, the reductive agent described in described step S4 is at least one in zinc powder, iron powder and hydrazine hydrate.
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